Catalytic reaction of hydrocarbons



Patented Dec. 3, 1940 l UNITED STATES PATENT oFFICEyZ No Drawing. Application May 18, 1938, Serial No. 208,695. In Great Britain May 25, 1937 Claims. (Cl. 260-94) 7 I L I This invention relates to the catalytic polymer- (6) Metal sulphides as prepared by Methods isation of hydrocarbons or of mixtures of hydro- Nos. 1-4 are mechanically mixed with, a; carrier carbons. substance. j]

As regards catalysts, the invention is concerned (7) v A carrier substance wetted with the solu- 5 with metal sulphide catalysts, and has for its obtion of a metal salt or containing adry metal salt ject to provide improved polymerisation processes or metal filings may be subjected under reactive employing activated metal sulphide catalysts. conditions to a stream of gaseous H28.

The invention consists briefly in a catalytic process for the production of hydrocarbons of ACTIVATION 0F {JATALYSTS relatively high molecular weight from hydrocar- The following methods can be listed .toactivate 10 bans of lower molecular weight by p01ymerisa .the catalysts. Other methods, however, by which tion in which the polymerisation is effected in heavy metal sulphides can be converted into 5111' the presence of a heavy metal sulphide activated Phatesv by which Oxygen mightwbecome 16 by association with sulphate. sorbed on a metal sulphide or dissolved in'a 131 ill hid, htals beuseful. PREPARATION, ACTIVATION AND APPLICA- me a s p 8 mg 0 'IION OF METAL SULPHIDE CATALYSTS Method 1 PREPARATION OF CATALYSTS Metal sulphides prepared according to any of the processes 1 to 7 above, or mixtures of such 20 metal sulphides, with or without carrier substances, are-treated with oxygen or air for instance durlng two months at room temperature. The treatment can be carried out at room temmg the sulphides mentioned perature or at higher temperature, at low or 2-.) (1) Soluble salts of heavy metals, for example,

high pressures, and using either wet or dry metal, cu, Fe, Ni, Co, Tl, B1, Pb, Mn, Hg, Mo, Cd, Zn, sulphides or mixtures Sn, Ge or Sb are treated in aqueous solutions either with 1128 or with another water soluble e o 2 sulphide Addltion? may be made of The metal sulphides or mixtures of sulphides ganic or organic acid or base, or of orgamc comprepared by any of the Seven above methods are 30 pounds such as unsaturated aldehydes, alcohols, mechanically mixed with heavy metal sulphates ketones or starch before HzS is applied. The or with mixtures of heavy metal sulphates, or heavy metal sulphides thus formed are either 161- with Sulphuric acid using either wet or dry tered oil or separated from the solution as by stances 20 I will first describe how sulphides may be prepared among other ways for use in connection with the present invention, but I am not suggesting that these are novel methods of preparcentrifugal action. E A pL-s FAP LICA'I'ION 35 (2) Metal filings are mixed with sulphur pow- X M 0 P 1 f t der and heated in vacuo, or they are treated with In an the following examp re erences o gaseous Hzs at reactive temperatures. parts are to parts by weight, and references to (3) Colloidal solutions of heavy metals and of temperatures are to In Examples E 40 Sulphur are mixedh to G, (Nos. 1-8) and H to S the reactants were 40 (4) Oxides, chlorides or bromides are treated enclosed in tubes and kept for some time at an under. reactive conditions with His This elevated temperature. In these cases the volume method can be ed for the preparation of the of the tubes was about 25 times that of the resulphides or V, Nb, 1, r Th, W or actants. At the end of the experiment the tubes (5) Soluble metal salts are treated in aqueous were Opened, and the contents subjected. solution with carrier substances such as active to fractmnate distma'tion' The technique (if carbon, carbonates, oxides, sulphates, silica gel, the measurements mentioned Example A is pumice stone, infusorial earth or like compounds described in thesis P Khmuntil absorption equilibrium is established. ms ham presented the Universlty i or other water soluble sulphides are introduced, March 1938 The i g f a i j f i 50 and the heavy metal sulphide is precipitated at of Examples C and D S escr e n e ouma' the surface of the carrier substance. The metal of the Chemical society 1936 page sulphide thus formed together with the carrier EXAMPLE A substance is separated from the solution, as in This example involves a synthetic process in No. 1. which more complex molecules are formed from 55 relatively simple molecules. The reaction is the ethylene were heated during sixty hours at 100 without catalysts or with 1 part cusoisrno or withlpart CuS containing 66.8% Cu and33.1 S.

Nodiamylene could be isolated. When the catalyst was a mechanical mixture of 0.8 part CuS (as above) and 0.2 part CuSO45I-IzO or 0.1 part o sulphuric .acid 2.7 parts diamylene were obtained.

EXAMPLE B Catalyst (a) CuS prepared from CuSO4 and H28 was kept under N2 during two months, at about Catalyst (b) CuS, same sample as above, was exposed to air during two months, at about 20.

9 parts trimethylethylene+1 part catalyst (41) were heated during 64 hours at 100". No diamylene could be isolated.

9 parts trimethylethylene-l-l part catalyst (b) were heated as above.

2 parts of diamylene were obtained.

Under the conditions of Examples 18 and C both CuS04 without CuS and CuO with or without CuS were catalytically inactive.

EXAMPLE C This example shows the catalytic efllciency of various heavy metal sulphides. The catalysts for this example have been prepared according to Examples 1 and 5 of "Preparation of Catalysts above in the presence of atmospheric oxygen so that free sulphur and sulphate are produced, because atmospheric oxygen, in the presence of salts of heavy metals, oxidises both hydrogen sulphide and water soluble sulphides to sulphate and sulphur. The reaction dealt with in this example is a typical diene synthesis or IDiels- Alder reaction, namely, the dimerisation of cyclopentadiene (CsHs) in paraflin solution. The product of the reaction is dicyclopentadiene (CioHizl parts of a 1.4 molar solution and 0.6 part of catalyst were used in each run; tempera- EXAMPLE E.--Polymer'lsafl0n of symmcthyl-cthul-ethylone 9 parts of methyl-ethyl-ethylene were heated at the temperatures and during the times given below.

The catalyst in No. 1 .was freshly prepared Irom (NI-102$ and SeSO4 and contained some moisture; the catalysts in Nos. 2, 3 and 4 were commercial samples, and the catalyst in No. 3 was prepared from @804 and H28 in said solution, and activated by exposure to air.

The catalyst in No. 3 was previously used in Experiment No. 2. It can be seen that the emciency of the catalyst in producing the high boiling products increases after continuous use. EXAMPLE F.--Polym emstlon of butodiene 9 parts of liquid butadiene were heated at 100 C. and 150 during 65 hours with a Gas catalyst prepared from CuS04 and H25 in acid solution and activated by exposure to air. At 100 0.1 part of a liquid of boiling point 110-120 were obtained. At 150 n0 liquid could be isolated but 3.1 parts of a very elastic rubber were produced. In the control without catalyst only 2 parts of ture 155. much less elastic rubber were isolated.

Catalyst None 0118 Q ms F08 8115 The Bus; rbs ri s Blmoleculu rate constant (1.1;. mol. mln.) 2 6 '5 6 5 4 5 6 6 EXAMPLE.D

This example shows the influence or various carrier substances in accordance with the conditions of Example 0. The catalysts for this example may be prepared as referred to in Example C above. Again the atmospheric oxygen produces a small amount of free sulphur and sulphate, so that the catalysts are mixtures of copper-sulphide, carrier substance, copper sulphate and sulphur. In all cases 0.6 part of catalyst were used, the other conditions being the: same as in Example C.

None OuB- CuS- CuS- CuS- Catalyst charcoal A1101 MgO CaCOa Bimolecular rate constant (l./. mol. min.) '2 4 2 2 5 0.6 part CuS-charcoal or 0.6 part CuS-CaCO: are nearly as efllcient as 0.6 part CuS without carrier substance (of. Example C) CaCO: alone 'was' inemcient. Gus-A120: and CuS-MgO were ineflicie'nt, but this might be due to the fact that the amount of adsorbed catalyst was very small.

EXAMPLE G.Polymerisatlon of butylenes 9 parts or liquid butylenes were heated with the catalyst at the temperatures and during the times given below. For Nos. 1-4 normal butylene was used, and for Nos. 5-8 isobutylene prepared from tertiary butyl-alcohol and sulphuric acid.

T Tim 1 $3558. i i": em e n u pon o WP hours Catalyst parts by produotin weight "0 1;... 150 65 Commercial 3.3 86-125 1 Gus oi anoth- 0. 3 125445 or firm activaied izy exposure our.

8 150 65 CuS prepared '22 -130 from 01180 0.7 130-175 and (NHOIS andex air during one month.

The catalyst in ExperimentNo. 3 was previously used for another experiment involving a butylene-trimethyl-ethylene mixture, and the catalyst in No. 4 was not previously used. It can be seen that the efliciency oi the catalyst increases after continuous use. 7

20.6 parts of a polymerlsed isobutylene fraction boiling between 85 and 140 C. were re-distilled and 15 parts boiling between and C. could be isolated. 7.0 parts of a polymerised isobutylene traction boiling between 125 and 183 were re-distilled, and 3.9 parts boiling between 130 and 175 C. were obtained. As the boiling point of dibutylene (CaHie) is about 100 I the boiling point of tributylene (C12H24) is about 180 0., it can be concluded that the polymerised butylenes referred to are probably largely dibutylenes and tributylenes.

This conclusion is confirmed by the analysis of the carbon and hydrogen content, by molecular weight determinations and by determinations oi the number of the double bonds.

40 parts of copper sulphideactivated by exposure to air are introduced in a tubing which is open at both ends and heated at l80-200. 0.8 part of gaseous butylene (of atmospheric pressure) prepared from normal butyl-alcohol pass per hour through this tubing. e products are dibutylene and tr ibutyiene in a yield of 0.4 part per hour.

EXAMPLE H.-Polgmerlaation of propylene 9 parts ofpropylene were heated at 150 .C. during 64 hours with a Cus catalyst prepared from CuSO; and H28 and activated by exposure to air. In,ai1 the following examples such'a catalyst is designated activated 0118." 0.1 part by weight of a liquid of boiling point 60-65 was obtained. 0 Y

EXAMPLE I.Polymerisation of ethylene 9 parts of ethylene were heated at 200 100 hours with activated CuS. weight of a liquid of boiling point obtained. EXAMPLE J.-Polymerisation,of a mimture of methylcthyl-ethylen'e and trimethyl-ethy'lene 13.5 parts of methy1-ethyl-ethylene and 4.5 parts by weight of trimethyl-ethyiene were heated during 65 hours with "activated CuS at the durin 0.1 part by 50-150 was temperatures given below.

.{Amoamtt Bailing! 0 pro uc pon 0 Temp" in parts by product.

weight C.

0., and

' introduced in a tubing EXAMPLE x z o lgzlgmtioa fl g oz lggre of meflwb 13.5 parts by weight of methyl-ethyl-ethylene and 4.5 parts by weight of isobutylene were heated with "activated CuS during 64 hours at 150 C. The product contained 7.5 parts of boiling point 3055, 2.4 parts of boiling point 95-130 and 0.3 part of boiling point -145". EXAMPLE L.-Polymerisatton of a miaiture of butylene and ieobutylene 13.5 parts .oi' butylene and 4.5 parts of isobutylene were heated with activated Gus at 150 C. during '64 hours. The product contained 3.5 parts of boiling point 75-110" and 1.6 parts of boiling point 110-210".

EXAMPLE M.-Polymerieutlon of a mimture of isobutulene and butadiene 13.5 parts of isobutylene and 4.5 parts of butadiene were heated with activated Gus" at 100 during 65 hours. The product contained 0.2 part oi boiling point 7o-9o and much rubber.

FXAMPLE N Po yrgzgisggzzv; 1:167? mlwture of prppglene 13.5 parts of propylene and 4.5 parts by weight of isobutylene were heated with "activated CuS at 150 .C. during 65 hours. tained 0.9 part of boiling point 64-93 C. and 0.6 part of boiling point 100-120 C.

EXAMPLE O.-Polymertaatlcn 05 a mixture of praylene and rrimethylet ylene 13.5 parts of propylene and 4.5 parts of trimethyl-ethylene were heated with activated (2118 at 150 C. during 64 hours. The product contained 1.3 parts of boiling point 42-65 C. and 0.3 part by weight of boiling point 70-120 C. EXAMPLE P. Pol1 men'eaton of a mixture of'trimethillethylene and pcntane I 13.5 parts of pentane and 4.5 parts by weight trimethylethylene were heated with activated CuS.during 65 hours. At 100 C. or at 150 C. the product contained 1.6 parts of boiling point C.

EXAMPLE Q.-Polymerisaton of a mimture of butylene and trimethylethglene Various quantities of normal butylenes and No. 4 was carried out as Nos. heating was finished 13.5 parts were added, and then the distillation of the product was carried out.

EXAMPLE R.--Polymersation of a mioture of isolwtylene and pentane 13.5 parts of pentane and 4.5 parts 01 iso- 1-3, but after the butylene were heated with "activated CuS during 66 hours at C. The product contained 0.6 part of boiling point 100-410 0.

weight of boiling point l10-l55 C.

EXAMPLE S.Pol1 merizctlon of acetylene copper sulphide are which is open on both 40 parts 01' activated" The product conof liquid butylene and 0.5 part by ends and heated at 180-200. 0.4 part of dry gaseous acetylene of atmospheric pressure pass per hour through this tubing over the catalyst. The product is cuprene which is. formed in a yield of 0.39 part per hour.

General used for all types of other Diels-Alder reaction sulphide.

or inverse Diels-Alder reactions.

All the reactions can occur either in the condensed or'inthe gaseous state, either at high or at low pressure, either athigh or at low temperatures. In many cases it might be useful to employ mixtures of catalysts men-.

specification dealing partly with what may be regarded as comparative tests, they do in fact form part of the invention.

, The catalysts described above are especially suitable for the conversion of olefinic or acetylenic gases either into hydrocarbons of moderately high molecular weight, boiling in the range of commercial fuels, or into hydrocarbons of high molecular weight, for example, rubber or resins. These components can either be prepared from pure hydrocarbons or from hydrocarbons dissolved in indifferent solvents or mixtures of solvents or from mixtures of hydrocarbons of relatively low molecular weight.

The butylenes referred to above can be prepared from butyl-alcohol according to known methods (cf. for instance the procedure of the British Patent No. 165,452 or of the American Patent No. 2,067,473). Water or some other compound, such for example as acetone, does not substantially or at all decrease the catalytic activity of the catalysts here described, and hence the conversion of butyl-alcohol or of butyl-alcohol-acetone mixtures into butylene polymersv can be carried out in one step'and in one apparatus by using a mixture of aluminium oxide or other metal oxides with activated heavy metal sulphides with or without carrier substances.

The metal sulphide used in any of the above examples may be replaced by other heavy metal sulphides or mixtures of such sulphides.

All the catalysts mentioned above may also be used in connection with mixtures consisting of more than two compounds.

I claim:

1. A process for the treatment of olefin hydrocarbons with a combined catalyst consisting of a heavy metal sulphide and a heavy metal sulphate, which said treatment comprises subjecting the olefins together with the aforesaid combined catalyst to a temperature less than about 200 C. and more than about 100 C., until a part of the olefins is converted into polymers the boiling point of which is at atmospheric pressure at least 50 C. higher than that of the starting material.

2. A process for the treatment of olefin hydrocarbons with a combined catalyst consisting of a heavy metal sulphide and a heavy metal sulphate, which said treatment comprises subjecting the olefins together with the aforesaid combined catalyst to a temperature less than about 200 C. and more than about 100 C., until a part of the olefins is converted into polymers which are liquid at room temperature and the boiling point of which is at atmospheric pressure at least 50 C. higher than that of the starting material.

*3. A process for the treatment of olefin hydrocarbons with a combined catalyst consisting of a heavy metal sulphide and a heavy metal sulphate, which said treatment comprises subjecting the olefins together with the aforesaid combined catalyst to 'a temperature less than about 200 C. and more than about 100 C., until a part of the olefins is converted into polymers which are solid at room temperature.

4. A process for the treatment of olefin hydrocarbons in admixture with a paraiiin hydrocarbon with a combined catalyst consisting of a heavy metal sulphide and a heavy metal sulphate, which said treatment comprises subjecting the mixture together with the aforesaid combined catalyst to a temperature less than about 200 C. and more than about 100 C., until a part of the starting material is converted into polymers which are liquid at room temperature and the boiling point of which is at atmospheric pressure at least 50 C. higher than that of the starting material.

5. A process for the treatment of olefin hydrocarbons in admixture with a paraffin hydrocarbon with a combined catalyst consisting of V a heavy metal sulphide and a heavy metal sulphate, which said treatment comprises subjecting .the mixture together with the aforesaid combined catalyst to a temperature less than about 200 C. and more than about 100 C., until a part of the starting material is converted into polymers which are solid at room temperature.

ALBERT WASSERMANN. 

